Desulphurizing petroleum oils



Jan. 28, 1936. F, M, ROGE'R'S 2,028,995

QESULPHURIZING PETROLEUM OILS Original Filed Dec. 15, 1928 Patented Jan. 28, 1936 Francis M. Borers, Wbi Standard Oil Company,v

poratlon or Indiana Application December 15, 1928.

' Renewed February 23,

Ind.,- glitnorto ting, d.,- a cor- 1' Claim. (q. lea-2r) I This invention relates to the 'desulphurfiatlon.

f livdrocarbon oils and particularly petroleum tillates of relatively low boiling point. I

Ihave discovered that if such distillates are vaporized and passed through adsorbent clay at a relatively h gh temperature, the sulphur content is, to a substantial extent, liberated from its combination in the hydrocarbon molecules and may readily be removed by treatment with smiles and m the like.

The method is particularly eilective in the case of straight run distillates which contain little or no unsaturated hydrocarbons. More effective desulphurization can be attained with the lower 15 boiling dlstillates, for example, gasoline, than with the higher boilingdistillates such as gas oil and the like.

The temperature at which the clay should be held lies within a broad range. Some sulphur is go removed at temperatures as low as 450 F. The

optimum temperature. is believed to be around 650 F., although higher temperatures of the orr der of 750 F. or more may be employed.

It is, however, preferred not to employ tem- 25 peratures above 750 F. because of complications due to cracking; Y

The inventionwill be more readily understood from the following description in conjunction with the accompanying drawing, which shows dia- 30 grammatically a suitable apparatus for carrying.

out the process.

Referring to the drawing, I is a molten metal bath containing lead or other readily fusible metal or alloy. The bath i0 is located in a suitable setas ting u and is adapted to be heated by a burner.

I! or other suitable heating means. Within the bath I0 is located a coil II which issupplied with distillate through its inlet H. The outlet I! of the 'coil l3 leads into a receptacle l6 which is 40 adapted to contain a substantial quantity of fullers earth or other suitable adsorbent clay, designated II. The outlet It leads into one end of the container 16, for example, the upper end,

as shown in the drawing. From the opposite end 45 of the container ii, that is, the lower end, as shown in the drawing, an outlet pipe l8 leads to a suitable condenser !9 which is connected to a receiver 20, provided with valved outlets 2'! so that the whole apparatus may be maintained un- 50- der atmospheric, superatmospheric, orsubatmospheric'pressure, as desired.

Where it is desired to operate under reduced pressure, the outlet 2| is connected to a suitable "vacuum pump (not shown). The clay ll may.

it be suitably supported upon a perforated false bottom 22 in the container I 6. The container I6 is located in a suitable setting 23 provided with burners 24 whereby the clay may be maintained at the desired temperature.

The operation of the process will be described by means of a specific example. Straight run gasoline derived from Winkler crude oil, of end point 420 F., containing 0.19%-

' sulphur and not treated with sulphuric acid or sweetened is passed through the coil l3, completely vaporized therein and brought to a temperature of approximately 650 F. The vapors are passed immediately into the chamber l6 which is substantially filled with raw 30-00 mesh Attapulgus clay maintained at a temperature of 650 to 700 F. throughout. After passing through the clay the vapors are condensed in the condenser l9 and cooled in the receiver 20. The rate of flow is approximately 12 barrels of gasoline per hour per ton of clay. I The condensed treated gasoline '20 is subjected to a wash with caustic soda solution to remove sulphuretted hydrogen which becomes disengaged during treatment, and is ready for use without doctor or sulphuric acid treatment.

Under the conditions indicated, the first condensate has a sulphur content of about 0.03%. The sulphur removal becomes progressivelyless complete but a yield of about 1400 barrels of gasoline per ton of clay may be obtained with an average sulphur content of about 0.06%. The 80 rate of feed may be increased to 20 barrels per hour per ton of clay with only slightly poorer yields and even higher rates may be used when less complete sulphur removal is permissible.

with Olmstead clay the initial sulphur removal is not as complete but the efliciency of this clay for a prolonged time is usually better than that of Attapulgus clay.

Similar runs with straight run gasoline from Panhandle crude all show a reduction of sulphur 40 content from 0.095% to 0.045% and with straight Winkler crude having a boiling range between 100 and 600 F. with new Olmstead clay at 650 F, the sulphur-content in the first runs is reduced from 0.3% to 0.14%. The 420 F. and point gasoline distilled from this product has a. sulphur content of 0.07%. A yield of about 2000 barrels l5 pertoncanbeobtained witniessmammiphura Pressure distillate derived mm z'as oil from the same crude subjected to liquid phase cracking operations of the"Holmes-Hanlay or Burton type, when treated in-the same manner shows even less complete sulphur removal although substantial'quantities of the contained which require the addition of considerable iree sulphur when sweetening with doctor. Such distillates must be redistilled after sweeteningand have a considerable te'ndency to become sour during re-runnlng becauseoi' the decomposition of disulphide's. The produt oi' the clay treatment appears to contain little or no disu1phides. In

the case of distillates or wide boiling range whlch redistilled to remove high boiling pointnacuons, the redist illation ay-be eifected with little orno steam without the product Although present invention has described in connection with the details of a specific example thereoi',itis to beimderstoodthat such 7 details are not intended to be limitative or the invention except in so far-as set forth in the accompa y n claim.- o

y In the claims hereinafter made, the term "solid adsorbent catalytic material or. the clay type" is intended to exclude pumice; activated charcoal,

'coke, siiica gel, fireclay and'the like, none of which resemble adsorbent clay.

I claim: The process or refining gasoline containing as impurities sulphur compounds difllcult to remove in theordinary manner which comprises convertin: said diiiicultly iremovable sulphur compounds into easily removable sulphur compounds by con-1 tacting said gasoline in the vapor form with solid adsorbent catalytic material oi. the clay type at a temperature of trom'650 to 750 1?. at a-flow rate of 12-to 20 barreisot oil per hour per vton .of catalyst, coolingand condensing the treated vapors and'treating them to remove said easily removable sulphur'compounds.

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